EP0422392A2 - Compound pieces of metal and rubber and method for manufacturing them - Google Patents

Compound pieces of metal and rubber and method for manufacturing them Download PDF

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Publication number
EP0422392A2
EP0422392A2 EP90117360A EP90117360A EP0422392A2 EP 0422392 A2 EP0422392 A2 EP 0422392A2 EP 90117360 A EP90117360 A EP 90117360A EP 90117360 A EP90117360 A EP 90117360A EP 0422392 A2 EP0422392 A2 EP 0422392A2
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EP
European Patent Office
Prior art keywords
rubber
parts
polyamide
weight
metal
Prior art date
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EP90117360A
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German (de)
French (fr)
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EP0422392A3 (en
Inventor
Hans Jadamus
Klaus-Peter Richter
Heinz Scholten
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Huels AG
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Huels AG
Chemische Werke Huels AG
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Publication of EP0422392A2 publication Critical patent/EP0422392A2/en
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/06—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of natural rubber or synthetic rubber
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B25/00—Layered products comprising a layer of natural or synthetic rubber
    • B32B25/14—Layered products comprising a layer of natural or synthetic rubber comprising synthetic rubber copolymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties

Definitions

  • the invention relates to composite parts which each consist of at least one metal and one rubber component and which contain an adhesion-promoting polyamide layer and a method for producing such parts.
  • the polyamide is applied either by the electrostatic powder coating method or by the whirl sintering method. It is also possible to apply the polyamide in the manner of a lacquer or by extrusion coating, but these methods are less advantageous.
  • the suitable powder coating methods are e.g. B. by R. Feldmann in company publication No. 5215 of Hüls AG, D-4370 Marl, from November 1987. Coat me Until now, processing methods have served to protect the metal surface against corrosion; the use as an adhesion promoter for rubbers, as described here, is new.
  • the rubbers below can be used for the process according to the invention. These rubbers have to be crosslinked peroxidically or by other radical additives. Crosslinkers based on sulfur or sulfur donors alone are not suitable for the process.
  • Workpieces made of steel are preferably used as the metallic component, but iron or non-ferrous metals such as aluminum or brass can also be used.
  • the surfaces can e.g. B. pretreated by degreasing, sandblasting or phosphating. Priming, as is often considered necessary with polyamide powder coatings, is superfluous here.
  • PA 1012, PA 11, PA 12 and PA 1212 are preferably used as polyamide (PA).
  • the polyamide is used as a powder.
  • the grain diameter can be up to 200 ⁇ m.
  • the polyamide can optionally additives such.
  • B. contain catalysts, stabilizers or pigments. Procedure for The production of suitable polyamides is known (R. Vieweg / A. Müller, Kunststoff Handbuch, Vol. 6 - Polyamid, C. Hanser Verlag Kunststoff 1966, p. 187; DE Floyd, Polyamide Resins, 2nd edition, Chapman Hall New York / London 1966 , P. 55).
  • polyamide powders for coatings is e.g. B. described in the German patent applications DE-OSS 35 10 687, 35 10 688, 35 10 689, 35 10 690 and 35 10 691 (corresponds to the European patent applications EP-OSS 0 202 393, 0 199 000, 0 200 853, 0 200 852 and 0 202 389).
  • the rubber compositions used contain: - 100 parts by weight of a rubber containing carboxyl groups or anhydride groups - 10 to 300 parts by weight of aggregates - 1 to 10 parts by weight of peroxidic vulcanizing agents - 0.5 to 4 parts by weight of vulcanization activators and - 0 to 150 parts by weight of plasticizer
  • the rubber used can also be a mixture of various suitable types. EP (D) M and NBR rubbers are preferably used.
  • the EPM rubber is produced in a known manner by polymerizing a mixture of 25 to 75% ethylene and 75 to 25% propylene in the presence of a Ziegler-Natta catalyst.
  • the EPDM rubber is made in an analogous manner by polymerizing a mixture more than 25% ethylene, more than 25% propylene and 1 to 10%, especially 1 to 3%, of a diene produced. This diene should not be conjugated.
  • the carboxylation of the EP (D) M rubbers takes place, for. B. in a known manner by compounding unsaturated acids or acid derivatives such as maleic acid or maleic anhydride (MA), optionally in the presence of a radical initiator.
  • unsaturated acids or acid derivatives such as maleic acid or maleic anhydride (MA)
  • MA maleic acid or maleic anhydride
  • Suitable manufacturing methods are e.g. B. specified in US Pat. No. 4,010,223.
  • Such carboxylated EPM rubbers are used for.
  • a suitable EPDM rubber has been found e.g. B. Maleic anhydride modified BUNA R AP (product name: "VESTAMID X 4496") from Bunawerken Hüls GmbH, D-4370 Marl.
  • NBR nitrile rubbers
  • the nitrile rubbers are known to be produced by copolymerization of 50 to 80 percent by weight of butadiene and correspondingly 50 to 20 percent by weight of acrylonitrile. A particular modification is formed by the nitrile rubbers containing carboxyl groups. These are copolymers of butadiene, acrylonitrile and acrylic acid, methacrylic or sorbic acid.
  • the vulcanizates of such mixtures are characterized by high tensile strength, good elasticity and very good abrasion resistance.
  • the oil and solvent resistance typical of nitrile rubber remains unchanged.
  • Suitable carboxylated NBR rubbers are e.g. B. from GOODYEAR TIRE & RUBBER Company, Akron, Ohio, USA, under the name CHEMIGUM R NX 775 or from BF GOODRICH, NV, Arnhem, Netherlands, under the trade name HYCAR R 1472.
  • Suitable additives are all fillers customary for EP (D) M and NBR rubbers such as. B. carbon black, silica, silicates and calcium carbonates as well as zinc oxide and stearic acid.
  • Suitable plasticizers are in particular mineral oils or synthetic plasticizers such as esters and ethers.
  • preference is given to using mineral oils, in particular naphthenic oils.
  • the amount of plasticizer can be up to 150 parts by weight, based on 100 parts by weight of rubber; preferably up to 50 parts by weight.
  • Suitable peroxidic vulcanizing agents are the peroxides known to the person skilled in the art, such as, for. B. 2,5-dimethyl-2,5-bis (tert-butylperoxy) hexane, dicumyl peroxide, 4,4-di-tert-butylperoxy-n-butylvalerate, 1,1-di-tert.butylperoxy-3.3. 5-trimethyl-cyclohexane and bis (tert-butylperoxyisopropyl) benzene. Details on the use of peroxidic vulcanizing agents can be found in the company brochure "Rubbery Chemical-Crosslinking-Peroxides" from Akzo-Chemie (publication date: April 1985).
  • Suitable vulcanization activators are, for example, triallyl cyanurate (TAC) and acrylates such as ethylene glycol dimethacrylate (EDMA) and trimethylolpropane trimethacrylate (TRIM). TAC and / or EDMA are preferably used.
  • TAC triallyl cyanurate
  • EDMA ethylene glycol dimethacrylate
  • TAM trimethylolpropane trimethacrylate
  • the composite parts are produced by vulcanizing the rubbers mentioned in close contact, preferably under pressure, with the polyamide-coated metals.
  • the vulcanization conditions are in themselves identical to the conditions that are used when using conventional adhesion promoters.
  • the vulcanization is preferably carried out at temperatures between 140 and 200 ° C. in 2 to 30 minutes, in particular at temperatures between 150 and 180 ° C. in 5 to 10 minutes.
  • Typical composite parts made of metals and rubber are e.g. B. rubber-coated rollers, seals, flanges, buffers, spring elements, vibration dampers, metal-reinforced rubber profiles, clutch and brake discs.
  • a particular advantage of such components is their resistance to corrosive media, especially corrosive salts.
  • EXXELOR R VA 1803 is a maleic anhydride-modified EPM rubber from Exxon Chemicals, Wilmington, Delaware, USA. The properties of the product can be found in the Technical Information EXXELOR VA "dated March 1st, 1988. ZnO is available under the name zinc white red seal from Grillo-Werke AG, D-3380 Goslar. VULKASIL R C is a highly active silica, available from Bayer AG, D-5090 Leverkusen. CIRCOSOL R 4240 is a predominantly naphthenic mineral oil from Sun Oil, Antwerp (Belgium).
  • VULKANOX R HS is an anti-aging agent from Bayer AG, D-5090 Leverkusen. It is 2,2,4-trimethyl-1,2-dihydroquinoline.
  • PERKADOX R 14/40 and PERKADOX R BC 40 are peroxides from Akzo-Chemie, 3800 AZ-Amersfoort, the Netherlands.
  • TAC triallyl cyanurate
  • EDMA ethylene glycol dimethacrylate
  • CHEMIGUM R NX 775 is a carboxyl group-containing NBR rubber from Goodyear Tire and Rubber, Akron, Ohio, USA. The properties of the product are listed in the product information "CHEMIGUM R NX 775", November 1987.
  • Example 1 (with a carboxylated EPM rubber)
  • a 1 mm thick steel sheet is heated in a heating oven at 400 ° C. for 10 minutes and immersed in a fluidized bed covered with commercially available coating powder from the brand for 10 seconds VESTOSINT R 1101 is filled with white. The coated steel sheet is allowed to cool.
  • Example 2 (with a carboxylated NBR rubber)

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Abstract

2.1. The object of the invention was substantially to simplify and to make more environment-friendly the conventional inconvenient production of such components. 2.2. The object was achieved by I. coating the metal part with a polyamide which serves as an adhesion promoter, preferably by a powder coating method, and II. then vulcanising a rubber mixture, which contains carboxylated rubber, in close contact with the polyamide-coated metal. 2.3. The composite articles are used for industrial purposes, for example as rollers, seals or vibration dampers.

Description

Die Erfindung betrifft Verbundteile, die aus mindestens je einer Metall- und einer Gummikomponente bestehen und die eine haftvermit­telnde Polyamidschicht enthalten sowie ein Verfahren zur Herstel­lung solcher Teile.The invention relates to composite parts which each consist of at least one metal and one rubber component and which contain an adhesion-promoting polyamide layer and a method for producing such parts.

Bekanntlich kann ein einziger Werkstoff nicht immer alle Eigen­schaften beitragen, die von einem Gegenstand verlangt werden. Nicht vereinbar sind z. B. hohe Festigkeit, Steifigkeit oder Härte einer­seits und gute Schwingungsdämpfung, Schmiegsamkeit oder Rutsch­festigkeit andererseits. Soll ein Körper diese Eigenschaften vereinen, dann verwendet man Verbunde aus mehreren Werkstoffen.As is well known, a single material cannot always contribute all the properties required of an object. Are not compatible z. B. high strength, rigidity or hardness on the one hand and good vibration damping, pliability or slip resistance on the other. If a body is to combine these properties, then composites made of several materials are used.

Es bietet sich an, in diesem Fall Metall und Gummi zu verwenden. Bauteile herzustellen, deren Komponenten Metall und Gummi fest mit­einander verbunden sind, geht man nach dem heutigen Stand der Tech­nik wie folgt vor:

  • 1. Die metallische Komponente wird z. B. durch Gießen, Pressen, Spanen oder Ziehen geformt.
  • 2. Die Oberfläche der metallischen Komponente wird z. B. durch Entfetten, Sandstrahlen, Vermessingen oder Phosphatieren behan­delt.
  • 3. Ein "Primer" wird aus einer Lösung z. B. in Aromaten oder Chlorkohlenwasserstoffen aufgetragen.
  • 4. Das Lösemittel wird durch Verdampfen entfernt.
  • 5. Ein "Haftvermittler" wird aus einer Lösung z. B. in Aromaten oder Chlorkohlenwasserstoffen aufgetragen.
  • 6. Das Lösemittel wird durch Verdampfen entfernt.
  • 7. Der Kautschuk wird auf die so vorbehandelte Metalloberfläche aufgebracht und ausvulkanisiert.
In this case, it makes sense to use metal and rubber. To produce components, the components of which are firmly connected to each other, metal and rubber, the current state of the art is as follows:
  • 1. The metallic component is z. B. formed by casting, pressing, machining or drawing.
  • 2. The surface of the metallic component is z. B. treated by degreasing, sandblasting, brassing or phosphating.
  • 3. A "primer" is z. B. applied in aromatics or chlorinated hydrocarbons.
  • 4. The solvent is removed by evaporation.
  • 5. An "adhesion promoter" is from a solution such. B. applied in aromatics or chlorinated hydrocarbons.
  • 6. The solvent is removed by evaporation.
  • 7. The rubber is applied to the metal surface pretreated in this way and vulcanized.

Die zwischen Metall und Kautschuk bzw. Gummi haftvermittelnden Stoffe werden z. B. in W. Kleemann, Mischungen für die Elastverar­beitung, Leipzig 1982 sowie im Bayer-Taschenbuch für die Gummi-In­dustrie, 1963, sowie besonders in Firmenschriften der Henkel KGaA unter dem Handelsnamen "Chemosil" beschrieben.The materials that promote adhesion between metal and rubber or rubber are, for. B. in W. Kleemann, mixtures for elast processing, Leipzig 1982 and in the Bayer paperback for the rubber industry, 1963, as well as in particular in company publications of Henkel KGaA under the trade name "Chemosil".

Die bekannten Verfahren sind aus verschiedenen Gründen verbesse­rungswürdig:

  • 1. Sie sind umständlich, wie aus der Aufzählung der vielen Verar­beitungsschritte hervorgeht.
  • 2. Sie sind hinsichtlich der Umweltbelastung und der Gesundheits­gefährdung am Arbeitsplatz nicht unbedenklich: die Lösemittel sind nicht harmlos und müssen entsorgt werden.
  • 3. Die Lagerfähigkeit der behandelten Metallkomponenten ist be­grenzt.
  • 4. Der Prozeß ist nicht automatisierbar.
The known methods can be improved for various reasons:
  • 1. They are cumbersome, as can be seen from the list of the many processing steps.
  • 2. They are not harmless with regard to environmental pollution and health risks at the workplace: the solvents are not harmless and must be disposed of.
  • 3. The shelf life of the treated metal components is limited.
  • 4. The process cannot be automated.

Es wurde nun gefunden, daß man auf die konventionellen Haftvemitt­ler und Primer mit Vorteil verzichten kann, wenn man die Metall­oberfläche in an sich bekannter Weise mit Polyamiden beschichtet, bevor man sie mit bestimmten Kautschukzusammensetzungen in Kontakt bringt.It has now been found that conventional adhesives and primers can advantageously be dispensed with if the metal surface is coated in a manner known per se with polyamides before it is brought into contact with certain rubber compositions.

Das Polyamid wird entweder nach dem Verfahren der elektrostatischen Pulverbeschichtung oder nach dem Verfahren des Wirbelsinterns auf­gebracht. Es ist auch möglich, das Polyamid in Art eines Lackes oder durch Extrusionsbeschichtung aufzutragen, doch sind diese Ver­fahren weniger vorteilhaft. Die geeigneten Pulverbeschichtungsver­fahren werden z. B. von R. Feldmann in der Firmenschrift Nr. 5215 der Hüls AG, D-4370 Marl, vom November 1987 beschrieben. Beschich­ tungsverfahren dienten bisher dem Schutz der Metalloberfläche gegen Korrosion; die Verwendung als Haftvermittler für Kautschuke, wie hier beschrieben, ist neu.The polyamide is applied either by the electrostatic powder coating method or by the whirl sintering method. It is also possible to apply the polyamide in the manner of a lacquer or by extrusion coating, but these methods are less advantageous. The suitable powder coating methods are e.g. B. by R. Feldmann in company publication No. 5215 of Hüls AG, D-4370 Marl, from November 1987. Coat me Until now, processing methods have served to protect the metal surface against corrosion; the use as an adhesion promoter for rubbers, as described here, is new.

Die Verwendung von Polyamiden als Haftvermittler zwischen Metallen und Kautschuk bzw. Gummi bietet eine Reihe von Vorteilen gegenüber den konventionellen Verfahren:

  • 1. Die ökologischen und hygienischen Probleme entfallen, da keine Lösemittel verwendet werden.
  • 2. Die mit dem haftvermittelnden Polyamid behandelten Metallteile sind praktisch unbegrenzt lagerfähig.
  • 3. Der Prozeß ist automatisierbar.
The use of polyamides as adhesion promoters between metals and rubber or rubber offers a number of advantages over the conventional processes:
  • 1. The ecological and hygienic problems are eliminated since no solvents are used.
  • 2. The metal parts treated with the adhesion-promoting polyamide can be stored practically indefinitely.
  • 3. The process can be automated.

Für das erfindungsgemäße Verfahren können die untenstehenden Kau­tschuke eingesetzt werden. Diese Kautschuke müssen peroxidisch oder durch andere radikalisch wirkende Additive vernetzt werden. Vernet­zer auf Basis von Schwefel oder Schwefelspendern allein eignen sich für das Verfahren nicht.The rubbers below can be used for the process according to the invention. These rubbers have to be crosslinked peroxidically or by other radical additives. Crosslinkers based on sulfur or sulfur donors alone are not suitable for the process.

Als metallische Komponente dienen vorzugsweise Werkstücke aus Stahl, es können aber auch Eisen oder Nichteisenmetalle wie Aluminium oder Messing eingesetzt werden. Die Oberflächen können z. B. durch Entfetten, Sandstrahlen oder Phosphatieren vorbehandelt werden. Ein Primern, wie es häufig bei Polyamidpulverbeschichtungen als notwendig erachtet wird, ist hier überflüssig.Workpieces made of steel are preferably used as the metallic component, but iron or non-ferrous metals such as aluminum or brass can also be used. The surfaces can e.g. B. pretreated by degreasing, sandblasting or phosphating. Priming, as is often considered necessary with polyamide powder coatings, is superfluous here.

Als Polyamid (PA) wird vorzugsweise PA 1012, PA 11, PA 12 und PA 1212 eingesetzt. Besonders bevorzugt ist PA 12 mit einer relativen Viskosität in m-Kresol (bestimmt nach den in DIN 53 727 beschriebe­nen Bedingungen) von 1.4 bis 2.0, vorzugsweise von 1.5 bis 1.7. Das Polyamid wird als Pulver eingesetzt. Der Korndurchmesser kann bis zu 200 µm betragen. Das Polyamid kann ggf. Additive wie z. B. Kata­lysatoren, Stabilisatoren oder Pigmente enthalten. Verfahren zur Herstellung geeigneter Polyamide sind bekannt (R. Vieweg/A. Müller, Kunststoffhandbuch, Bd. 6 - Polyamid, C. Hanser Verlag München 1966, S. 187; D. E. Floyd, Polyamide Resins, 2. Auflage, Chapman Hall New York/London 1966, S. 55).PA 1012, PA 11, PA 12 and PA 1212 are preferably used as polyamide (PA). PA 12 with a relative viscosity in m-cresol (determined according to the conditions described in DIN 53 727) from 1.4 to 2.0, preferably from 1.5 to 1.7, is particularly preferred. The polyamide is used as a powder. The grain diameter can be up to 200 µm. The polyamide can optionally additives such. B. contain catalysts, stabilizers or pigments. Procedure for The production of suitable polyamides is known (R. Vieweg / A. Müller, Kunststoff Handbuch, Vol. 6 - Polyamid, C. Hanser Verlag Munich 1966, p. 187; DE Floyd, Polyamide Resins, 2nd edition, Chapman Hall New York / London 1966 , P. 55).

Die Herstellung von Polyamidpulvern für Beschichtungen ist z. B. in den deutschen Offenlegungsschriften DE-OSS 35 10 687, 35 10 688, 35 10 689, 35 10 690 und 35 10 691 beschrieben (entspricht den europäischen Offenlegungsschriften EP-OSS 0 202 393, 0 199 000, 0 200 853, 0 200 852 und 0 202 389).The production of polyamide powders for coatings is e.g. B. described in the German patent applications DE-OSS 35 10 687, 35 10 688, 35 10 689, 35 10 690 and 35 10 691 (corresponds to the European patent applications EP-OSS 0 202 393, 0 199 000, 0 200 853, 0 200 852 and 0 202 389).

Die verwendeten Kautschukzusammensetzungen enthalten:
- 100 Gewichtsteile eines Carboxylgruppen bzw. Anhydridgruppen enthaltenden Kautschuks
- 10 bis 300 Gewichtsteile Zuschlagstoffe
- 1 bis 10 Gewichtsteile peroxidischer Vulkanisations­mittel
- 0,5 bis 4 Gewichtsteile Vulkanisationsaktivatoren und
- 0 bis 150 Gewichtsteile WeichmacherThe rubber compositions used contain:
- 100 parts by weight of a rubber containing carboxyl groups or anhydride groups
- 10 to 300 parts by weight of aggregates
- 1 to 10 parts by weight of peroxidic vulcanizing agents
- 0.5 to 4 parts by weight of vulcanization activators and
- 0 to 150 parts by weight of plasticizer

Der verwendete Kautschuk kann auch eine Mischung verschiedener geeigneter Typen sein. Bevorzugt werden EP(D)M- und NBR-Kautschuke eingesetzt.The rubber used can also be a mixture of various suitable types. EP (D) M and NBR rubbers are preferably used.

Der EPM-Kautschuk wird in bekannter Weise durch Polymerisation eines Gemisches aus 25 bis 75 % Ethylen und 75 bis 25 % Propylen in Gegenwart eines Ziegler-Natta-Katalysators hergestellt.The EPM rubber is produced in a known manner by polymerizing a mixture of 25 to 75% ethylene and 75 to 25% propylene in the presence of a Ziegler-Natta catalyst.

Der EPDM-Kautschuk wird in analoger Weise durch Polymerisation eines Gemisches aus
mehr als 25 % Ethylen,
mehr als 25 % Propylen und
1 bis 10 %, insbesondere 1 bis 3 %, eines Diens
hergestellt. Dieses Dien sollte nicht konjugiert sein. Man bevor­ zugt Bicyclo(2.2.1)heptadien, Hexadien-1.4, Dicyclopentadien und insbesondere 5-Ethylidennorbornen.The EPDM rubber is made in an analogous manner by polymerizing a mixture
more than 25% ethylene,
more than 25% propylene and
1 to 10%, especially 1 to 3%, of a diene
produced. This diene should not be conjugated. One before adds bicyclo (2.2.1) heptadiene, hexadiene-1.4, dicyclopentadiene and especially 5-ethylidene norbornene.

Die Carboxylierung der EP(D)M-Kautschuke erfolgt z. B. in bekannter Weise durch Eincompoundierung von ungesättigten Sauren bzw. Säure­derivaten, wie Maleinsäure oder Maleinsäureanhydrid (MSA), gege­benenfalls in Anwesenheit eines Radikalstarters. Geeignete Her­stellmethoden sind z. B. in der US-PS 4 010 223 angegeben.The carboxylation of the EP (D) M rubbers takes place, for. B. in a known manner by compounding unsaturated acids or acid derivatives such as maleic acid or maleic anhydride (MA), optionally in the presence of a radical initiator. Suitable manufacturing methods are e.g. B. specified in US Pat. No. 4,010,223.

Derartige carboxylierte EPM-Kautschuke werden z. B. von der Fa. EXXON unter der Bezeichnung EXXELORR VA 1803 hergestellt. Als geeigneter EPDM-Kautschuk erwies sich z. B. maleinsäureanhydrid­modifiziertes BUNAR AP (Produktbezeichnung: "VESTAMID X 4496") von den Bunawerken Hüls GmbH, D-4370 Marl.Such carboxylated EPM rubbers are used for. B. manufactured by EXXON under the name EXXELOR R VA 1803. A suitable EPDM rubber has been found e.g. B. Maleic anhydride modified BUNA R AP (product name: "VESTAMID X 4496") from Bunawerken Hüls GmbH, D-4370 Marl.

Die Nitril-Kautschuke (NBR) werden bekannterweise durch Copolymeri­sation von 50 bis 80 Gewichtsprozent Butadien und entsprechend 50 bis 20 Gewichtsprozent Acrylnitril hergestellt. Eine besondere Mo­difikation bilden die Carboxylgruppen enthaltenden Nitrilkautschu­ke. Es handelt sich hier um Mischpolymerisate aus Butadien, Acryl­nitril und Acrylsäure, Methacryl- oder Sorbinsäure.The nitrile rubbers (NBR) are known to be produced by copolymerization of 50 to 80 percent by weight of butadiene and correspondingly 50 to 20 percent by weight of acrylonitrile. A particular modification is formed by the nitrile rubbers containing carboxyl groups. These are copolymers of butadiene, acrylonitrile and acrylic acid, methacrylic or sorbic acid.

Die Vulkanisate solcher Mischungen zeichnen sich durch eine hohe Zugfestigkeit, gute Elastizität und sehr guten Abriebwiderstand aus. Die für Nitrilkautschuk typische Öl- und Lösemittelbeständig­keit bleibt unverändert.The vulcanizates of such mixtures are characterized by high tensile strength, good elasticity and very good abrasion resistance. The oil and solvent resistance typical of nitrile rubber remains unchanged.

Geeignete carboxylierte NBR-Kautschuke werden z. B. von GOODYEAR TIRE & RUBBER Company, Akron, Ohio, USA, unter der Bezeichnung CHEMIGUMR NX 775 oder von BF GOODRICH, NV, Arnheim, Niederlande, unter dem Handelsnamen HYCARR 1472 hergestellt.Suitable carboxylated NBR rubbers are e.g. B. from GOODYEAR TIRE & RUBBER Company, Akron, Ohio, USA, under the name CHEMIGUM R NX 775 or from BF GOODRICH, NV, Arnhem, Netherlands, under the trade name HYCAR R 1472.

Als Zuschlagstoffe eignen sich alle für EP(D)M- und NBR-Kautschuke üblichen Füllstoffe wie z. B. Ruß, Kieselsäure, Silikate und Calcium-Carbonate sowie Zinkoxid und Stearinsäure.Suitable additives are all fillers customary for EP (D) M and NBR rubbers such as. B. carbon black, silica, silicates and calcium carbonates as well as zinc oxide and stearic acid.

Geeignete Weichmacher sind insbesondere mineralische Öle oder synthetische Weichmacher wie Ester und Ether. Hierbei werden im Falle des EP(D)M-Kautschuks vorzugsweise mineralische Öle, insbe­sondere naphthenische Öle eingesetzt. Die Weichmachermenge kann bis zu 150 Gewichtsteilen, bezogen auf 100 Gewichtsteile Kautschuk, betragen; vorzugsweise bis zu 50 Gewichtsteilen.Suitable plasticizers are in particular mineral oils or synthetic plasticizers such as esters and ethers. In the case of EP (D) M rubber, preference is given to using mineral oils, in particular naphthenic oils. The amount of plasticizer can be up to 150 parts by weight, based on 100 parts by weight of rubber; preferably up to 50 parts by weight.

Geeignete peroxidische Vulkanisationsmittel sind die dem Fachmann bekannten Peroxide wie z. B. 2,5-Dimethyl-2,5-bis(tert.-butylper­oxy)hexan, Dicumylperoxid, 4,4-Di-tert.-butylperoxy-n-butylvalerat, 1,1-Di-tert.butylperoxy-3.3.5-trimethyl-cyclohexan und Bis(tert.-­butylperoxyisopropyl)benzol. Einzelheiten zum Einsatz von peroxidi­schen Vulkanisationsmitteln sind der Firmenbroschüre "Rubbery Che­mical-Crosslinking-Peroxides" der Akzo-Chemie (Erscheinungsdatum: April 1985) zu entnehmen.Suitable peroxidic vulcanizing agents are the peroxides known to the person skilled in the art, such as, for. B. 2,5-dimethyl-2,5-bis (tert-butylperoxy) hexane, dicumyl peroxide, 4,4-di-tert-butylperoxy-n-butylvalerate, 1,1-di-tert.butylperoxy-3.3. 5-trimethyl-cyclohexane and bis (tert-butylperoxyisopropyl) benzene. Details on the use of peroxidic vulcanizing agents can be found in the company brochure "Rubbery Chemical-Crosslinking-Peroxides" from Akzo-Chemie (publication date: April 1985).

Als Vulkanisationsaktivatoren eignen sich beispielsweise Triallyl­cyanurat (TAC) und Acrylate wie Ethylenglykoldimethacrylat (EDMA) und Trimethylolpropantrimethacrylat (TRIM). Bevorzugt werden TAC und/oder EDMA eingesetzt.Suitable vulcanization activators are, for example, triallyl cyanurate (TAC) and acrylates such as ethylene glycol dimethacrylate (EDMA) and trimethylolpropane trimethacrylate (TRIM). TAC and / or EDMA are preferably used.

Die Herstellung der Verbundteile geschieht durch Vulkanisation der genannten Kautschuke in engem Kontakt, vorzugsweise unter Druck, mit den polyamidbeschichteten Metallen. Die Vulkanisationsbedin­gungen sind an sich identisch mit den Bedingungen, die bei Verwen­dung konventioneller Haftvermittler angewendet werden. Vorzugsweise wird die Vulkanisation bei Temperaturen zwischen 140 und 200 °C in 2 bis 30 Minuten, insbesondere bei Temperaturen zwischen 150 und 180 °C in 5 bis 10 Minuten durchgeführt.The composite parts are produced by vulcanizing the rubbers mentioned in close contact, preferably under pressure, with the polyamide-coated metals. The vulcanization conditions are in themselves identical to the conditions that are used when using conventional adhesion promoters. The vulcanization is preferably carried out at temperatures between 140 and 200 ° C. in 2 to 30 minutes, in particular at temperatures between 150 and 180 ° C. in 5 to 10 minutes.

Typische Verbundteile aus Metallen und Gummi sind z. B. gummibe­schichtete Walzen, Dichtungen, Flansche, Puffer, Federelemente, Schwingungsdämpfer, metallverstärkte Gummiprofile, Kupplungs- und Bremsscheiben. Ein besonderer Vorteil solcher Bauteile ist ihre Beständigkeit gegenüber korrosiven Medien, besonders korrosiven Salzen.Typical composite parts made of metals and rubber are e.g. B. rubber-coated rollers, seals, flanges, buffers, spring elements, vibration dampers, metal-reinforced rubber profiles, clutch and brake discs. A particular advantage of such components is their resistance to corrosive media, especially corrosive salts.

Zur Erläuterung der Erfindung dienen die nachstehenden Beispiele. Dort werden folgende Substanzen eingesetzt:
EXXELORR VA 1803 ist ein maleinsäureanhydrid-modifizierter EPM-Kau­tschuk der Fa. Exxon Chemicals, Wilmington, Delaware, USA. Die Ei­genschaften des Produktes sind der Technischen Information EXXELOR VA" vom 01.03.1988 zu entnehmen.
ZnO ist unter der Bezeichnung Zinkweiß Rotsiegel der Fa. Grillo-­Werke AG, D-3380 Goslar zu beziehen.
VULKASILR C ist eine hochaktive Kieselsäure, erhältlich bei der Bayer AG, D-5090 Leverkusen.
CIRCOSOLR 4240 ist ein vorwiegend naphthenisches Mineralöl der Fa. Sun Oil, Antwerpen (Belgien).
VULKANOXR HS ist ein Alterungsschutzmittel der Bayer AG, D-5090 Leverkusen. Es handelt sich um 2,2,4-Trimethyl-1,2-dihydrochinolin.
PERKADOXR 14/40 und PERKADOXR BC 40 sind Peroxide der Fa. Akzo-Chemie, 3800 AZ-Amersfoort, Niederlande.
TAC (Triallylcyanurat) und EDMA (Ethylenglykoldimethacrylat) sind Produkte der Fa. Degussa, D-6450 Hanau.
CHEMIGUMR NX 775 ist ein Carboxylgruppen enthaltender NBR-Kautschuk der Fa. Goodyear Tire and Rubber, Akron, Ohio, USA. Die Eigenschaf­ten des Produkts sind in der Produktinformation "CHEMIGUMR NX 775", November 1987, aufgeführt.The examples below serve to illustrate the invention. The following substances are used there:
EXXELOR R VA 1803 is a maleic anhydride-modified EPM rubber from Exxon Chemicals, Wilmington, Delaware, USA. The properties of the product can be found in the Technical Information EXXELOR VA "dated March 1st, 1988.
ZnO is available under the name zinc white red seal from Grillo-Werke AG, D-3380 Goslar.
VULKASIL R C is a highly active silica, available from Bayer AG, D-5090 Leverkusen.
CIRCOSOL R 4240 is a predominantly naphthenic mineral oil from Sun Oil, Antwerp (Belgium).
VULKANOX R HS is an anti-aging agent from Bayer AG, D-5090 Leverkusen. It is 2,2,4-trimethyl-1,2-dihydroquinoline.
PERKADOX R 14/40 and PERKADOX R BC 40 are peroxides from Akzo-Chemie, 3800 AZ-Amersfoort, the Netherlands.
TAC (triallyl cyanurate) and EDMA (ethylene glycol dimethacrylate) are products from Degussa, D-6450 Hanau.
CHEMIGUM R NX 775 is a carboxyl group-containing NBR rubber from Goodyear Tire and Rubber, Akron, Ohio, USA. The properties of the product are listed in the product information "CHEMIGUM R NX 775", November 1987.

Beispiel 1 (mit einem carboxylierten EPM-Kautschuk)Example 1 (with a carboxylated EPM rubber)

Ein 1 mm dickes Stahlblech erhitzt man in einem Wärmeofen während 10 Minuten auf 400 °C und taucht es während 10 Sekunden in ein Wir­belbett, das mit käuflichem Beschichtungspulver der Marke VESTOSINTR 1101 weiß gefüllt ist. Das beschichtete Stahlblech läßt man erkalten. Man legt das polyamidbeschichtete Stahlblech in einen 4 mm dicken Distanzrahmen, bedeckt ein Drittel des Blechs fit einer Teflonfolie, um an dieser Stelle eine Haftung zu verhindern, be­schichtet Blech und Trennfolie mit einem Fell bestehend aus EXXELORR VA 1803 100 Teile ZnO 5 Teile VULKASILR C 60 Teile CIRCOSOLR 4240 40 Teile VULKANOXR HS 2 Teile PERKADOXR 14/40 7,5 Teile TAC 3 Teile und preßt die Komposition 20 Minuten bei 170 °C und 200 bar. Metall und Gummi sind nach dieser Behandlung nur durch kohäsiven Bruch im Gummi voneinander zu trennen.A 1 mm thick steel sheet is heated in a heating oven at 400 ° C. for 10 minutes and immersed in a fluidized bed covered with commercially available coating powder from the brand for 10 seconds VESTOSINT R 1101 is filled with white. The coated steel sheet is allowed to cool. Place the polyamide coated steel sheet in a 4 mm thick spacer frame, cover a third of the sheet with a Teflon film to prevent adhesion at this point, coat the sheet and separating film with a skin consisting of EXXELOR R VA 1803 100 parts ZnO 5 parts VULKASIL R C 60 parts CIRCOSOL R 4240 40 parts VULKANOX R HS 2 parts PERKADOX R 14/40 7.5 parts TAC 3 parts and presses the composition for 20 minutes at 170 ° C and 200 bar. After this treatment, metal and rubber can only be separated from one another by a cohesive break in the rubber.

Beispiel 2 (mit einem carboxylierten NBR-Kautschuk)Example 2 (with a carboxylated NBR rubber)

Man verfährt wie in Beispiel 1, verwendet aber eine andere Kau­tschuk-Mischung: CHEMIGUMR NX 775 100 Teile Stearinsäure 1 Teile VULKASILR C 40 Teile PERKADOXR BC 40 3 Teile Aktivator EDMA 0,5 Teile Auch in diesem Verbundkörper sind Gummi und Metall nur durch kohä­siven Bruch im Gummi voneinander zu trennen.The procedure is as in Example 1, but a different rubber mixture is used: CHEMIGUM R NX 775 100 parts Stearic acid 1 parts VULKASIL R C 40 parts PERKADOX R BC 40 3 parts EDMA activator 0.5 parts In this composite body too, rubber and metal can only be separated from one another by a cohesive break in the rubber.

Claims (5)

1. Verbundteile, bestehend aus folgenden Komponenten: I. einem Metall; II. einer haftvermittelnden Polyamidschicht und III. einem Gummi, der durch Vulkanisation einer Kautschukmischung aus
- 100 Gewichtsteilen eines Carboxylgruppen bzw. Anhydridgruppen enthaltenden Kautschuks,
- 10 bis 300 Gewichtsteilen Zuschlagstoffen,
- 1 bis 10 Gewichtsteilen peroxidischer Vulkanisationsmittel,
- 0,5 bis 4 Gewichtsteilen Vulkanisationsaktivatoren sowie
- 0 bis 150 Gewichtsteile Weichmacher entstanden ist. 1. Composite parts, consisting of the following components: I. a metal; II. An adhesion-promoting polyamide layer and III. a rubber made by vulcanizing a rubber compound
100 parts by weight of a rubber containing carboxyl groups or anhydride groups,
- 10 to 300 parts by weight of aggregates,
1 to 10 parts by weight of peroxidic vulcanizing agents,
- 0.5 to 4 parts by weight of vulcanization activators as well
- 0 to 150 parts by weight of plasticizer has arisen. 2. Verbundteile gemäß Anspruch 1,
dadurch gekennzeichnet,
daß das Polyamid aus der Reihe PA 1012, PA 11, PA 12 und PA 1212 ausgewählt ist.2. composite parts according to claim 1,
characterized,
that the polyamide is selected from the PA 1012, PA 11, PA 12 and PA 1212 series. 3. Verbundteile gemäß Anspruch 2,
dadurch gekennzeichnet,
daß das Polyamid ein PA 12 mit einer relativen Viskosität von 1,4 bis 2,0, vorzugsweise 1,5 bis 1,7 ist.3. composite parts according to claim 2,
characterized,
that the polyamide is a PA 12 with a relative viscosity of 1.4 to 2.0, preferably 1.5 to 1.7. 4. Verbundteile gemäß den Ansprüchen 1 bis 3,
dadurch gekennzeichnet,
daß der Carboxyl- bzw. Anhydridgruppen enthaltende Kautschuk ein carboxylierter EPM-, EPDM- und/oder NBR-Kautschuk ist.4. composite parts according to claims 1 to 3,
characterized,
that the rubber containing carboxyl or anhydride groups is a carboxylated EPM, EPDM and / or NBR rubber. 5. Verfahren zur herstellung der Verbundteile gemäß den Ansprüchen 1 bis 4,
dadurch gekennzeichnet,
daß I. das Metallteil mit einem Polyamid beschichtet wird; II. anschließbend die Vulkanisation der Kautschukmischung in engem Kontakt mit dem polyamidbeschichteten Metall er­folgt. 5. A method for producing the composite parts according to claims 1 to 4,
characterized,
that I. the metal part is coated with a polyamide; II. The vulcanization of the rubber mixture then takes place in close contact with the polyamide-coated metal.
EP19900117360 1989-10-12 1990-09-10 Compound pieces of metal and rubber and method for manufacturing them Withdrawn EP0422392A3 (en)

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DE3934090A DE3934090A1 (en) 1989-10-12 1989-10-12 COMPONENTS OF METALS AND RUBBER AND METHOD FOR THE PRODUCTION THEREOF
DE3934090 1989-10-12

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EP0822064A2 (en) * 1996-08-02 1998-02-04 ENICHEM S.p.A. Polyamide and acrylic rubber munufactured products and process for their preparation
DE19640180A1 (en) * 1996-09-30 1998-04-09 Freudenberg Carl Fa Process for the production of a rubber-metal part
WO1999055793A1 (en) * 1998-04-23 1999-11-04 Advanced Elastomer Systems, L.P. Metal reinforced thermoplastic elastomers
WO2008147955A1 (en) * 2007-05-24 2008-12-04 Lord Corporation Powder adhesives for bonding elastomers
WO2011002672A1 (en) * 2009-06-30 2011-01-06 The Gates Corporation Bonded part with laminated rubber member and method of making
EP2202058A3 (en) * 2001-01-15 2011-08-17 Daicel-Evonik Ltd. Composite material and method for preparation thereof
EP2537672A1 (en) * 2010-02-15 2012-12-26 The Yokohama Rubber Co., Ltd. Bonded body composed of carbon thin film-coated article and rubber
US8709195B2 (en) 2008-11-07 2014-04-29 Lord Corporation Powdered primer for rubber to metal bonding

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CA2295836A1 (en) 1997-12-24 1999-07-08 Mikuni Plastics Co., Ltd. Pipe made of rigid thermoplastic resin, pipe joint structure and their manufacturing method
US6800372B2 (en) 2001-01-16 2004-10-05 Daicel-Degussa Ltd. Composite and process for producing the same
DE10115510B4 (en) * 2001-03-28 2006-11-16 Linie M - Metall Form Farbe-Gmbh Game apparatus or seating for public facilities and method of making the same
JP3898584B2 (en) 2002-07-03 2007-03-28 ダイセル・デグサ株式会社 Resin composition, composite using the same, and method for producing the same
JP2004043670A (en) 2002-07-12 2004-02-12 Daicel Degussa Ltd Complex dispersion and its preparation method

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EP0335642A2 (en) * 1988-04-01 1989-10-04 Nichias Corporation Vibration damping materials and soundproofing structures using such damping materials

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0822064A3 (en) * 1996-08-02 1999-06-23 Zeon Chemicals Incorporated Polyamide and acrylic rubber munufactured products and process for their preparation
EP0822064A2 (en) * 1996-08-02 1998-02-04 ENICHEM S.p.A. Polyamide and acrylic rubber munufactured products and process for their preparation
DE19640180A1 (en) * 1996-09-30 1998-04-09 Freudenberg Carl Fa Process for the production of a rubber-metal part
DE19640180C2 (en) * 1996-09-30 1999-07-01 Freudenberg Carl Fa Process for producing a rubber-metal part and use of the process
WO1999055793A1 (en) * 1998-04-23 1999-11-04 Advanced Elastomer Systems, L.P. Metal reinforced thermoplastic elastomers
EP2202058A3 (en) * 2001-01-15 2011-08-17 Daicel-Evonik Ltd. Composite material and method for preparation thereof
EP2813534A3 (en) * 2001-01-15 2015-03-11 Daicel-Evonik Ltd. Composite and process for producing the same
WO2008147955A1 (en) * 2007-05-24 2008-12-04 Lord Corporation Powder adhesives for bonding elastomers
US8709195B2 (en) 2008-11-07 2014-04-29 Lord Corporation Powdered primer for rubber to metal bonding
WO2011002672A1 (en) * 2009-06-30 2011-01-06 The Gates Corporation Bonded part with laminated rubber member and method of making
CN102802936B (en) * 2009-06-30 2015-02-11 盖茨公司 Bonded part with laminated rubber member and method of making
CN102802936A (en) * 2009-06-30 2012-11-28 盖茨公司 Bonded Part With Laminated Rubber Member And Method Of Making
EP2537672A4 (en) * 2010-02-15 2013-09-04 Yokohama Rubber Co Ltd Bonded body composed of carbon thin film-coated article and rubber
US8691386B2 (en) 2010-02-15 2014-04-08 The Yokohama Rubber Co., Ltd. Bonded body of a carbon thin film covered article and a rubber
EP2537672A1 (en) * 2010-02-15 2012-12-26 The Yokohama Rubber Co., Ltd. Bonded body composed of carbon thin film-coated article and rubber

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PT95549A (en) 1991-08-14
JPH03133631A (en) 1991-06-06
EP0422392A3 (en) 1991-12-04
DD298076A5 (en) 1992-02-06
DE3934090A1 (en) 1991-04-18
CA2027210A1 (en) 1991-04-13

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